EP0134756A2 - Compositions containing a copolymerisate and a tensioactive agent, their use and preparation - Google Patents

Abstract

The invention relates to preparations containing oil, polymers and surfactants which (a) contain a water-soluble cationic copolymer composed of 0.2-9 mol% of monomers of the formula (I) and 91 to 99.8 mol% of acrylic and / or methacrylamide (b) anionic surfactant wherein the molar fraction of anionic surfactant (b) is not greater than the molar fraction of cationic monomer units of the copolymer (a), and (c) water-immiscible oils in which the polymer is not soluble but is finely divided therein contain and optionally contain other additives, in particular (d) oil-soluble, non-ionic surfactants (e) water and (f) polar oil-soluble solvents which are not self-dispersible in water and are very slightly soluble in water and also have no emulsifier properties on their own , but lower the interfacial tension water oil; the invention further relates to the preparation of the preparations, their dilution, the use of the preparations as flocculants and the production of paper by salting in such flocculants.

Description

Hydrophilic, i.e. Cationic polymers which are soluble or dispersible in water are nowadays used in industry as flocculants, e.g. for the production of paper, are increasingly used and are often handled in the form of aqueous preparations, in particular also of W / 0 emulsions. For example, cationic acrylamide copolymers as flocculants, etc. used for the production of paper; an important area of application is their use as retention agents in papermaking. It has already been proposed to prepare cationic acrylamide copolymers with different levels of cationic comonomers (for example in CA Patents 1 110 019 and 1 133 788, in Japanese Kokai 57-128 293 and in US Pat. No. 4,037,040) and as flocculants, e.g. also to be used as a retention aid for papermaking (as in CA-PS 1 133 788 or in Japanese Kokai 57-128 293); In the case of the cationic acrylamide copolymers described there, it can be found that as the mole fraction of cationic comomers in the copolymer decreases, the effect as a retention agent for paper also decreases.

It has now been found that when a certain choice of cationic copolymers is combined with a certain very low proportion of the cationic comomers with certain surfactants and certain oils, surprisingly good retention aids - in particular as W / 0 emulsions - can be obtained for paper production, in which the retention effect in this low cationicity range unexpectedly increases again.

The invention relates to such oil-containing preparations, their preparation, their dilution with water and their use and the products obtained by using the preparations.

• (a_l) Acryl- und/oder Methacrylamid
• und (a₂) einem Monomeren der Formel
  
• worin R₁ Wasserstoff oder Methyl,
• R2 Methyl oder Aethyl,
• R₃ Methyl oder Aethyl
• und n 2 oder 3
• bedeuten,

A first subject of the invention is therefore water-dilutable preparations containing oil, polymer and surfactant, which are characterized in that they comprise a cationic copolymer as polymer (a)

• (a _l ) acrylic and / or methacrylamide
• and (a ₂ ) a monomer of the formula
  
• wherein R _{1 is} hydrogen or methyl,
• R2 methyl or ethyl,
• R _{3 is} methyl or ethyl
• and n 2 or 3
• mean,

contain, the molar fraction of (a _l ) in the copolymer making up 91 to 99.8 mol% and the molar fraction (a ₂ ) in the copolymer making up the remaining 9 to 0.2 mol%,

contain an anionic surfactant as surfactant (b), the molar fraction of anionic surfactant (b) being not greater than the molar fraction of cationic monomer units of the copolymer (a) and part of the cationic monomer units of the copolymer combined with the anionic surfactant for salt formation can be

and contain as oil (c) a water-immiscible oil in which the polymer is not soluble but is finely divided.

The hydrophilic copolymers (a) are cationic, ie they are free from anionic monomer components, or they can be obtained by polymerizing exclusively the cationic monomers (a ₂ ) and the nonionic monomers (a _l ).

• worin A⊖ ein Gegenion zur Ammoniumgruppe ist.
• R₁ steht vorzugsweise für Methyl.
• R₂ steht vorzugsweise für Methyl.
• R₃ steht vorzugsweise für Methyl.
• Der Index n steht vorzugsweise für 3.

The monomers of the formula (I) can also be in protonated form and then correspond to the formula

• wherein A⊖ is a counter ion to the ammonium group.
• R ₁ preferably represents methyl.
• R ₂ preferably represents methyl.
• R ₃ preferably represents methyl.
• The index n is preferably 3.

The symbol generally stands for any anion, as is customary for ammonium compounds, advantageously for a halide ion (in particular chloride) or sulfate anion. In a particular embodiment of the invention, A⊖ also stands for (A ₁ ) ⊖, ie for the anion of the anionic, advantageously lipophilic, preferably oil-soluble surfactant (b) as defined below.

The proportion of cationic monomer units in the copolymers to be used according to the invention is advantageously 1 to 8 mol%, preferably 2 to 6 mol% of the total copolymer.

The average molecular weight (weight average) of the copolymers to be used according to the invention can be as high as desired, advantageously up to 20,000,000; they advantageously have an average molecular weight ^k 500,000, preferably ≽ 1,000,000. The average molecular weight is preferably in the range from 1,000,000 to 20,000,000.

• -sulfatoerte Fettsäuremone-, -di- und -triglyceride (insbesondere sulfatierte, natürliche Fette oder Oele und sulfatierte Monoglyceride), sulfatierte Fettalkohole und sulfatierte Fettsäurealkanolamide;
• - sulfonierte Kohlenwasserstoffe, vornehmlich Alkylsulfonate, Olefinsulfonate und Alkylarylsulfonate, insbesondere Petroleumsulfonate; sulfonierte aliphatische Carbonsäuren und Carbonsäureester, insbesondere a-Sulfomonocarbonsäuren, a-Sulfomonocarbonsäureester und Sulfobernsteinsäurealkylester;
• - Phosphorsäurealkylpartialester;
• aliphatische Carbonsäuren (Seifen) und Carboxymethylierungsprodukte von Fettalkoholen, Monoglyceriden und Fettsäurealkanolamiden.

As component (b), ie as anionic surfactants, any customary surfactants are generally suitable which contain at least one lipophilic hydrocarbon radical and at least one hydrophilic anionic group, as described, for example, in "Surfactant Science Series" (M. Dekker Inc., New York and Basel), vol. 7: "Anionic Surfactants" (edited by Warner M. Linfield, 1976) - parts 1 and 2 -. the lipophilic radical is preferably araliphatic or aliphatic and advantageously contains min at least 9 carbon atoms, preferably 12-36 carbon atoms; the anionic group can be any customary acid group which is optionally in salt form, primarily carboxylate, phosphate, phosphonate, sulfate and sulfonate, of which carboxylate, phosphate, sulfate and sulfonate are preferred, but especially the sulfonate group; if appropriate, polyalkylene glycol ether groups may also be present in the molecule of the anionic surfactant, but the surfactants preferably do not contain any polyalkylene glycol ether groups. Individual, noteworthy classes of anionic surfactants are the following:

• sulfated fatty acid mono-, di- and triglycerides (especially sulfated, natural fats or oils and sulfated monoglycerides), sulfated fatty alcohols and sulfated fatty acid alkanolamides;
• - Sulfonated hydrocarbons, primarily alkyl sulfonates, olefin sulfonates and alkylarylsulfonates, especially petroleum sulfonates; sulfonated aliphatic carboxylic acids and carboxylic acid esters, especially a-sulfomonocarboxylic acids, a-sulfomonocarboxylic acid esters and alkyl sulfosuccinic acid esters;
• - phosphoric acid alkyl partial esters;
• aliphatic carboxylic acids (soaps) and carboxymethylation products of fatty alcohols, monoglycerides and fatty acid alkanolamides.

Among the anionic surfactants mentioned, the sulfonates, especially the sulfonated hydrocarbons, are preferred, especially petroleum sulfonates.

The anionic surfactants (b) are advantageously at least partially in the form of salt, any desired cations being possible for salt formation, for example alkali metal cations (lithium, sodium, potassium), ammonium cations [both unsubstituted ammonium and substituted ammonium, for example mono- , Di- and tri- (C _1-8 -alkyl) -ammonium and mono-, di- and tri- (C _2-3 -alkanol) -ammonium, in particular mono-, di- and triethylammonium, mono-, di - and triisopropanolammonium and mono, di and triethanol ammoniul, Erd alkali metal cations (magnesium, calcium, strontium and barium) and other multivalent cations, in particular Zn ²⁺ , A1 ³⁺ and Zr ⁴⁺ . The anionic surfactants are preferably in the form of the corresponding salts of polyvalent inorganic cations, of which calcium is particularly preferred.

The anionic surfactants can have a more or less pronounced water solubility or dispersibility or can be practically insoluble in water (ie they do not give any real solution in water at the concentrations used, but can still be dispersible in water and / or preferably in oil be dispersible or soluble), which essentially depends on the choice of the lipophilic residue and on the choice of the cation. Preferred anionic surfactants are the lipophilic, preferably those which are oil-soluble in the form of the Na salt, in particular those which are in the form of salts of such cations (preferably polyvalent inorganic cations) that they do not give any real solutions in water at the concentrations used and give W / O emulsions with water and with corresponding oils, especially as defined under (c), ie they have W / 0 emulsifier character or are W / O emulsifiers.

The above-mentioned anionic surfactants are generally known or can be prepared in a manner known per se. The amine salts and the salts of polyvalent inorganic cations of the anionic surfactants are advantageously prepared in situ by advantageously reacting the alkali metal salts of these surfactants with water-soluble salts of the corresponding amines or the polyvalent inorganic cations. As the water-soluble salts generally salts of strong inorganic acids and simple organic carboxylic acids (hydrochloric acid, nitric acid and phosphoric acid, depending on the cation advantageously sulfuric acid,) (C _l-4 carboxylic acids, especially formic acid and acetic acid) into consideration, wherein among the amine salts of the sulfates, Phosphates, chlorides and acetates are preferred and the formates and especially the chlorides are preferred among the salts of the polyvalent inorganic cations. Calcium chloride is particularly preferably used.

In general, the copolymers in the preparations according to the invention contain the cationic monomer units corresponding to the monomers (a ₂ ) and the non-ionic monomer units corresponding to the monomers (a _l ), part of the cationic monomer units, in particular containing the anion of the anionic surfactant as a counterion to the cation. The polymers can be represented schematically as those which contain the following recurring monomer units:

wherein A⊖ is an anion as defined above and R _{4 is} methyl or preferably hydrogen.

In aqueous preparations with acidic pH values or in the presence of the anionic surfactants, the cationic monomer units are preferably present as (ß ₂ ), in which part of A⊖ is the anion (A ₁ ) ⊖ of the anionic surfactant.

The anionic surfactant is advantageous

(bi) a lipophilic, preferably oil-soluble, anionic surfactant,

especially an oil-soluble hydrocarbon sulfonate.

Component (c) can be either a uniform oil or a mixture of different oils. In general, any oils such as are used for the production of water-soluble polymer-containing emulsions and / or dispersions are suitable, both natural and synthetic oils. Both natural oils from the processing of petroleum and vegetable and animal oils (essentially triglycerides) are suitable as natural oils; synthetic oils include both synthetic hydrocarbons and modified paraffins (hydrocarbons) and fatty acid esters (primarily triglycerides and monoesters).

• 1. Kohlenwasserstoffe
• 1.1 Kohlenwasserstoffe aus der Erdölverarbeitung, vornehmlich
• 1.1.1 Spezialbenzine, die aus dem Rohbenzin herausdestilliert werden (Siedebereich 65-140°C) (desaromatisierte, sowie aromatenhaltige Typen)
• 1.1.2 White Spirits, Testbenzine und Lackbenzine, (Siedebereich 100-310°C,- vorzugsweise 140-300°C), insbesondere:
  
• 1.1.3 Aromatenfreie Kohlenwasserstoffe mit isoparaffinischer Struktur (Siedebereich 110-260°C)
• 1.1.4 Paraffinöle (= Mineralöle) z.B. Dieselöle, Spindelöle, Maschinenöle, Zylinderöle, Schmieröle und Vaselinöle
• 1.1.5 Petrolatum (Petrolate)
• 1.2 Synthese Kohlenwasserstoffe, vornehmlich solche aus der Fischer-Tropsch-Synthese oder der Hochdruckkohlehydrierung, insbesondere:
  
• ₁.₃ Gegebenenfalls alkylsubstituierte Benzole, Benzol, Xylol, Toluol, _Methyläthyl- und Trimethylbenzole, Dimethyläthyl- und Tetramethylbenzole, sowie höhere Alkylbenzole (C₆-C_l2Alkylbenzole).
• 2. Natürliche vegetabile oder tierische Triglyceride insbesondere Olivenöl, Erdnussöl, Cottonöl, Kokosfett, Rüböl, Sonnenblumenöl, Maiskeimöl, Rizinusöl und Klauenöl.
• ₃. Fettsäure-monoester, vornehmlich C_l-₄-Alkylester von C12-24-, vorzugsweise C14-24-Fettsäuren, insbesondere: Methyl-, Butyl- und Isopropylester von Stearinsäure, Oelsäure, Palmitinsäure und Myristinsäure und deren Mischungen.

Individual, preferred categories of oils are the following:

• 1. hydrocarbons
• 1.1 Petroleum hydrocarbons, primarily
• 1.1.1 Special gasoline, which is distilled out of the raw gasoline (boiling range 65-140 ° C) (dearomatized and aromatic-containing types)
• 1.1.2 White spirits, white spirit and mineral spirits, (boiling range 100-310 ° C, - preferably 140-300 ° C), in particular:
  
• 1.1.3 Aromatic-free hydrocarbons with an isoparaffinic structure (boiling range 110-260 ° C)
• 1.1.4 Paraffin oils (= mineral oils) eg diesel oils, spindle oils, machine oils, cylinder oils, lubricating oils and petroleum jelly oils
• 1.1.5 Petrolatum (Petrolate)
• 1.2 Synthesis of hydrocarbons, primarily those from the Fischer-Tropsch synthesis or high-pressure coal hydrogenation, in particular:
  
• _{1st 3} optionally alkyl-substituted benzenes, benzene, xylene, toluene, _M ethyläthyl- and trimethylbenzenes, tetramethylbenzenes and Dimethyläthyl-, as well as higher alkyl benzenes (C ₆ -C _l2 alkyl benzenes).
• 2. Natural vegetable or animal triglycerides, in particular olive oil, peanut oil, cotton oil, coconut oil, rape oil, sunflower oil, corn oil, castor oil and claw oil.
• _3rd Fatty acid monoester, especially C _l - ₄ alkyl esters of C12-24-, preferably C14-24 fatty acids, in particular: methyl, butyl and isopropyl esters of stearic acid, oleic acid, palmitic acid and myristic acid and mixtures thereof.

The petrolates are advantageously used in a mixture with oils that are liquid at room temperature (20 ° C).

Among the oils mentioned, the largely aromatic-free hydrocarbons and the aliphatic fatty acid esters are preferred, in particular the hydrocarbons, including those according to sections 1.1.2, 1.1.3 and 1.1. ₄ , and especially aromatic-free and low-aromatic white spirits, iso-para _f finish oils (1.1.3) and mineral oils (1.1.4) are preferred.

If appropriate, (c) is a mixture of at least two oils, in particular a mixture of an oil (c _l ) and an oil (c ₂ ), which are chosen such _that the O / W-EHLB value of the oil (c _l ) is greater than the O / W-EHLB value of the mixture of oils (c _l ) ⁺ (c ₂ ). O / W-EHLB value means the optimal HLB value of a hypothetical surfactant which is required for this oil or oil mixture, so that a stable oil-in-water emulsion can form; see, for example, "Cosmetics, Science and Technology", John Wiley and Sons ( _2nd edition, vol. 3, 1974), pages 602-607, or Philip Sherman "Emulsion Science", Academic Press, London and New York, 1968, Pages 146-147, or Paul Becher "Emulsion, Theory and Practice", 2nd edition, 1965, American Chemical Society, Monograph Series no. 162.

The O / W-EHLB value of the oil (c ₂ ) is preferably smaller than that of the oil (c _l ).

Preferred oils (ci) have an O / W EHLB value in the range from 10 to 15; Such oils are among those listed above, in particular those mentioned in sections 1.1.1, 1.1.2, 1.1.3 and 1.3. Preferred oils (c ₂ ) have an O / W EHLB value of 7 to 10; such oils are, among those listed above, in particular those mentioned in sections 1.1.4, 1.1.5, 2 and 3.

• (d) ein lipophiles, vorzugsweise öllösliches, nicht-ionogenes Tensid.

The preparations according to the invention also advantageously contain

• (d) a lipophilic, preferably oil-soluble, non-ionic surfactant.

This component (d) can be a uniform surfactant or a mixture of lipophilic or oil-soluble, non-ionic surfactants. Component (d) is expediently a W / 0 (water-in-oil) emulsifier, i.e. a surfactant which is capable of producing a W / O emulsion with at least part of the oils (c) in the presence of water.

The non-ionic surfactants (d) are advantageously water-insoluble or only dispersible in water and, as W / O emulsifiers, advantageously have an HLB value ≼ 8, preferably between 3 and 8; the HLB value is particularly preferably between 4 and 7.

If (d) is a mixture of non-ionogenic lipophilic surfactants, the individual components of this mixture (d) can also have different HLB values, but are then preferably used in such relative amounts that the average HLB value of this surfactant mixture is advantageous ≼ 8 and is preferably between 3 and 8, in particular between 4 and 7.

• - Mono- oder Polyoxäthylierungs-und/oder Oxypropylierungsprodukte von gesättigten und/oder ungesättigten, linearen und/oder verzweigten aliphatischen Alkoholen, von Alkylphenolen, von Fettsäuren, von Fettsäurealkanolamiden, von Fettsäurepolyolpartialestern und von vegetabilen oder tierischen Fetten oder Oelen; bzw. entsprechende Verätherungs-und/oder Veresterungsprodukte von Mono- und/oder Polyäthylen- und/oder -propylenglykolen.
• - Fettsäurepolyolpartialester;
• - Nicht-ionogene Aethylenoxid/Propylenoxidcopolymerisate mit einem hohen Anteil an Propylenoxyeinheiten (Pluronic Typen) und Aethylenoxid/Propylenoxidadditionsprodukte an Aethylendiamin, mit einem hohen Anteil an Propylenoxyeinheiten (Tetronic Typen), die wegen des hohen Anteils an Propylenoxyeinheiten als nicht-ionogene Tenside gelten.

As component (d), ie as lipophilic, preferably oil-soluble, non-ionic surfactants, generally suitable compounds are suitable, essentially those which contain at least one lipophilic hydrocarbon radical, advantageously contain at least 9, preferably 9-24 carbon atoms and at least one non-ionogenic hydrophilic residue, which is advantageously a mono- or polyethylene glycol residue optionally containing propylene glycol units and / or the residue of a higher polyol (eg glycerol, mannitol, pentaerithritol or sorbitol); these lipophilic or oil-soluble surfactants can also be referred to as hydrophobic surfactants and among the hydrophobic surfactants also the hydrophobic pluronic types and tetronics can be mentioned, in which the high proportion of polypropylene glycol can be referred to as a lipophilic residue. The following categories of non-ionic surfactants can be mentioned:

• Mono- or polyoxyethylation and / or oxypropylation products of saturated and / or unsaturated, linear and / or branched aliphatic alcohols, of alkylphenols, of fatty acids, of fatty acid alkanolamides, of fatty acid polyol partial esters and of vegetable or animal fats or oils; or corresponding etherification and / or esterification products of mono- and / or polyethylene and / or propylene glycols.
• - fatty acid polyol partial esters;
• - Non-ionic ethylene oxide / propylene oxide copolymers with a high proportion of propyleneoxy units (Pluronic types) and ethylene oxide / propylene oxide addition products of ethylenediamine, with a high proportion of propyleneoxy units (Tetronic types), which are considered non-ionogenic surfactants due to the high proportion of propyleneoxy units.

The polyol partial esters mentioned are advantageously di- or preferably monoesters of aliphatic polyols with 3 or more hydroxyl groups, primarily glycerol, pentaerythritol, mannitol or sorbitol.

Preferred nonionic surfactants are generally mono- and / or polyoxyethylation products of aliphatic alcohols, of alkylphenols and of aliphatic fatty acids, polyol partial esters of aliphatic fatty acids, mono- and / or diethers of mono- and / or polyethylene glycols with ali phatic alcohols and / or alkylphenols and mono- and / or diesters of mono- and / or polyethylene glycols with aliphatic fatty acids.

The fatty acid residues which occur can generally be acyl residues of customary alkylcarboxylic acids or alkenylcarboxylic acids, monoethylenically unsaturated acids being advantageous as alkenylcarboxylic acids. The alkyl radicals as the only lipophilic radicals [(as for example in the formula (III) below] advantageously contain at least 9 carbon atoms, preferably 9-24 carbon atoms, in particular 9-18 carbon atoms and can be linear or branched. In the alkylaryl radicals, for example in the rest of the formula (y) below, the alkyl radicals advantageously contain 4-12 carbon atoms and can also be linear or branched .. If the lipophilic radical is the acyl radical of a carboxylic acid, then it is advantageously the radical of a fatty acid, essentially an alkyl or Alkenyl carboxylic acid, which advantageously contains 9-24, preferably 12-20, carbon atoms, with lauric acid, myristic acid, stearic acid and oleic acid being particularly preferred The polyethylene glycol derivatives, in particular also the formulas below, are generally average formulas, ie those in which the one given Number of ethyleneoxy units is an average number, too in the case of the lipophilic hydrocarbon radicals, mixtures e.g. Partial mixtures occur and in such a case the specified number of carbon atoms represents an average number.

und

worin R₅ C₉-₂₄-Alkyl oder -Alkenyl oder einen Rest der Formel

• R₆-CO- je den Acylrest einer Alkyl- oder Alkenylcarbonsäure mit
• 12-20 Kohlenstoffatomen,
• ^R7 ^C ₄-₁₂-Alkyl,
• X den q-wertigen Rest von Glycerin oder Sorbit oder eines Mono-oder Polyäthylenglykols der Formel
  
• p 1 bis 6,
• q 1 oder 2, oder bei Sorbit auch 3,
• r 1 oder 2
• und s 1 bis 10

Among the nonionic surfactants mentioned, those of the following formulas are particularly preferred:

and

wherein R ₅ is C _9-24 alkyl or alkenyl, or a radical of formula

• R ₆ -CO- each with the acyl radical of an alkyl or alkenyl carboxylic acid
• 12-20 carbon atoms,
• ^R 7 ^C ₄ - ₁₂ alkyl,
• X is the q-valent radical of glycerol or sorbitol or of a mono- or polyethylene glycol of the formula
  
• p 1 to 6,
• q 1 or 2, or 3 for sorbitol,
• r 1 or 2
• and s 1 to 10

mean, the number and length of the lipophilic radicals and number of -CH ₂ -CH ₂ -0 groups are expediently chosen so that the HLB value of the nonionic emulsifier or mixture of emulsifiers is between 3 and 8, preferably between 4 and 7 .

und

worin R₈ C_9-18-Alkyl oder -Alkenyl,

• Rg-CO- den Acylrest einer aliphatischen C_12-18-Fettsäure, Y- den einwertigen Rest von Sorbit, Glycerin oder Di- bis
• Tetraäthylenglykol,
• t 2 bis 3,
• k 3 bis 5
• und m 4 bis 9

bedeuten.Among them, those of the following formulas are particularly preferred

and

wherein R _{8 is} C _9-18 alkyl or alkenyl,

• Rg-CO- the acyl residue of an aliphatic C _12-18 fatty acid, Y- the monovalent residue of sorbitol, glycerol or di-
• Tetraethylene glycol,
• t 2 to 3,
• k 3 to 5
• and m 4 to 9

mean.

The HLB value of the nonionic surfactants can be calculated using a simple known formula, knowing the lipophilic residue of the hydrophilic residue and the number of ethyleneoxy or propyleneoxy units. If the calculated value for a non-ionic surfactant is 2.5 or less, then it is no longer considered a W / 0 emulsifier here.

If (c) is a mixture of oils (ci) and (c ₂ ), then the surfactants (d) and the oils are advantageously chosen such that the 0 / W-EHLB of the mixture (ci) ⁺ (c ₂ ) is as close as possible but the HLB value of (d) is advantageously not less than this.

• (e) Wasser.

The preparations according to the invention also advantageously contain

• (e) water.

The copolymers (a) or the salts thereof, which contain the anion of the anionic surfactant as counterion, are hydrophilic, i.e. they can absorb water or form a gel or sol in the presence of water or are at least colloidally soluble in water; the relative amount of water used with the oil (c) and with the emulsifier (d) is generally chosen so that the polymer is finely dispersed together with the water in the oil (whether as a suspension of the polymer with water taken up or of the water-swollen polymer or of the aqueous polymer gel in the oil, be it as an emulsion of the aqueous polymer sol or the aqueous polymer solution in the oil).

• (f) ein mit Oel mischbares, in Wasser schwerlösliches und nicht selbstdispergierbares, polares Lösungsmittel, das alleine keine Emulgatoreigen schaften aufweist, aber die Grenzflächenspannung Wasser/Oel erniedrigt, enthalten.

If necessary, the preparations according to the invention can additionally

• (f) a polar solvent which is miscible with oil, sparingly soluble in water and not self-dispersible, which alone has no emulsifier properties but lowers the interfacial tension water / oil.

These solvents are generally polar compounds which have an extremely low HLB value but are still sufficiently polar to attach to the oil / water interface; these are advantageously water-insoluble, aliphatic alcohols or phosphoric acid triesters or Pluronics. The alcohols advantageously contain 5-10 carbon atoms per hydroxyl group and the following can be mentioned in particular: methyl-isobutylcarbinol, 2-ethylhexanol, isononanol, isodecanol and 2,4,7,9-tetramethyl-5-decyn-4,7-diol . Among the phosphoric acid triesters, tributyl phosphate, triisobutyl phosphate and tri (butoxyethyl) phosphate can be mentioned in particular. Among the Pluronics, the Pluronic L101 can be mentioned in particular.

The terms "soluble", "dispersible" and "insoluble" are understood, of course, in such conditions (in particular concentrations or concentration ranges and temperatures or temperature ranges) as used here.

The invention further relates to the process for the preparation of the preparations according to the invention, which is characterized in that the copolymer (a) is combined with the surfactant (b) and the oil (c) before, during and / or after the copolymerization, wherein the copolymer or the corresponding monomers are preferably in the finest possible form.

If the copolymerization takes place in a W / O emulsion, it is advantageous that at least some of the surfactants, in particular the anionic surfactants, are added before the copolymerization and / or before the addition of the cationic monomer.

A particular object of the invention is the process for the preparation of preparations according to the invention, which is characterized in that the monomers required for forming the copolymers (a) are polymerized in the presence of the anionic surfactants (b) in a W / O emulsion and, if desired, water and / or distilled off oil and optionally further Additions (a), (b), (c), (d), (e) and / or (f), and / or further surfactants are added.

The vinyl-like monomers are advantageously emulsified in the form of an aqueous solution, advantageously in the presence of the anionic surfactants and preferably also in the presence of the nonionic, oil-soluble surfactants (d) in at least part of the oil (c), the cationic monomers being in a molar There is an excess over the anionic surfactants; the aqueous phase emulsified in oil may contain further additives, e.g. usual complexing agents, salts and acids and / or bases for pH adjustment. In a preferred process variant, the vinyl-like monomers to be polymerized are added to the submitted W / O emulsion, which already contains anionic surfactant and optionally non-ionic surfactant and / or other customary additives, or the vinyl-like monomers to be polymerized added to the aqueous dispersion (suspension and / or emulsion) or solution of the anionic surfactant, after which oil and optionally nonionic surfactant and / or other conventional additives can be added, or the monomers to be polymerized are dissolved in water and become this aqueous monomer solution given the surfactants (b) and (d) dissolved in the oil (c); the aqueous and / or the oily phase can contain further customary additives, such as complexing agents, salts and acids and / or bases for pH adjustment; this enables dispersions of the aqueous monomer phase to be produced in oil. Due to the presence of the anionic surfactants in the monomer-containing W / O emulsion, some of the cationic monomers, especially under neutral to acidic conditions, can be in the form of less water-soluble, lipophilic surfactant salts, in which the anion of the anionic surfactant acts as a counterion to the cationic monomer . After the initiator has been added, the emulsion polymerization can be carried out in a conventional manner.

A particular embodiment of the production process for the polymer-containing preparations according to the invention consists in that an oily dispersion comprising a hydrophilic, cationic copolymer (a), water (e) and a lipophilic or oil-soluble, non-ionic surfactant (d) but does not contain an anionic surfactant, and this is preferably mixed with a lipophilic, preferably oil-soluble, practically water-insoluble, anionic surfactant (b ₂ ), where (b ₂ ) is a sulfonated hydrocarbon, optionally in salt form, and the oil of the oily dispersion is an oil (c ₃ ) is a water-immiscible hydrocarbon oil in which the copolymer (a) is not soluble, but is finely distributed therein with the water. Suitable hydrocarbon oils (c ₃ ) are generally those as described in subsection 1.1, of which those according to corresponding subsections 1.1.1 to 1.1.4, in particular 1.1.3, 1.1.4 and especially white spirits are preferred.

The oily dispersions which contain (a) in addition to (e), (c ₃ ) and (d) but no (b), are advantageously obtained by emulsion polymerization of corresponding aqueous monomer solutions in oil and in the presence of the emulsifier (d) and, if appropriate, partial distillation of water prepared and can then be mixed with (b) or (b ₂ ) and optionally with hydrophilic emulsifiers.

The copolymerization can be carried out in a manner known per se (see, for example, “High Polymers”, vol. 9, 1955 “Emulsion Polymerization”, publisher: Interscience Publishers Inc., New York) and the aqueous system can, in addition to the particular constituents required according to the invention, Usual additives contain, such as polymerization initiators (preferably compounds which form free radicals under thermal decomposition or a redox system), complexing agents (e.g. disodium salt of ethylenediaminetetraacetic acid), acids and / or bases for pH adjustment and / or metal salts, for example Na ⁺ and / or Ca ^{2 +} salts. After inerting (ie after displacing the oxygen by means of inert gas) and after adding suitable polymerization initiators, the polymerization takes place. After emulsion polymerization has taken place, or in particular after bringing together anionic surfactants and cationic copolymers, cationic groups in the corresponding salt form can also be present in the copolymer, especially after dilution with water. The copolymerization is normally exothermic and is advantageously carried out under acidic conditions, for example at pH values between 2 and 6, preferably at pH values between 2.5 and 4. The water content of the W / 0-emulsion during the polymerization is advantageously 15-80%, preferably 30-75 wt% _`(based on the total emulsion). The polymerization can be carried out adiabatically or isothermally, but it is preferably carried out partially adiabatically, ie the temperature is allowed to rise to a limited extent by metered addition of the initiator and / or by cooling the reaction mixture, advantageously to values ≼ 120 ° C., if appropriate under pressure; the procedure is preferably between 30 and 110 ° C. If the mixture to be polymerized contains hydrolyzable monomers (in particular esters or primary amides), then such reaction conditions are expediently chosen that hydrolysis to the undesired acids is avoided as far as possible.

With the surfactants to be used according to the invention, very finely divided dispersions can be achieved even with relatively little surfactant. The emulsion polymerization enables very high molecular weights of the copolymers to be achieved, so that a very broad spectrum of molecular weights of the copolymers can be available, which also allows the preparations according to the invention to be used very widely.

The emulsion polymerization is advantageously carried out in the presence of at least some of the oils (c). Oils in which at least a part, preferably at least 50% by weight, particularly preferably at least 80% by weight, of hydrocarbons are advantageously used for the emulsion polymerization, preference being given to the largely aliphatic hydrocarbons. The relative amounts of water and oil and the concentration of the aqueous monomer solution can vary widely, with particularly good copolymers being obtained with relatively dilute monomer solutions and emulsions; the concentration of the total monomers in the W / O emulsion is advantageously 5 to 35%, preferably 10 to 30%; the weight ratio of water to oil is preferably kept as high as possible, as it is still sufficient for the emulsion to remain a W / O emulsion, and is advantageously 1.5 to 6, preferably 1.8 to 4.8; the W / O emulsion to be polymerized contains at least a portion of the surfactants (b) [preferably (b ₁ ) J and / or (d) as is sufficient to provide one sufficient for the polymerization enough stable W / O emulsion. After the polymerization has taken place, the copolymer-containing W / O emulsion obtained can be mixed with further additives - for example with further components (a), (b), (c), (d) and / or (e) and / or with the component ( f) - and / or the content of components (c) and / or (e) can be reduced, for example by distillation; these additional modifications of the copolymer-containing W / O emulsions can influence, in particular improve, the properties of the preparations, for example their stability and / or their dilutability with water.

If the preparation should also contain component (f), then this is advantageously added to the preparation as the last, or after emulsion polymerization has taken place; Conveniently, (f) is used in a form prediluted with a little oil (c), but if desired, larger amounts of oil (c) can also be used and / or, together with (f) or with its solution in oil (c), further ones can also be used Additions (a), (b), (d) and / or optionally (e) are added to the preparation.

If the preparation is to contain a mixture of oils (c ₁ ) and (c ₂ ), then the emulsion polymerization is advantageously carried out in oil (c _l ), which may contain (c ₂ ); The oil (c ₂₎ or the ev. remaining portion of the oil (c ₂₎ if necessary, can be added after the emulsion polymerization, optionally after distilling off the water, or of most of the water.

• x Gewichtsteile der Komponente (b)
• y Gewichtsteile der Komponente (c)
• z Gewichtsteile der Komponente (d)
• u Gewichtsteile der Komponente (e) und
• v Gewichtsteile der Komponente (f).

The quantitative composition of the preferred preparations according to the invention and obtainable as described above can advantageously be schematized as follows: the preparation contains per 100 parts by weight of component (a)

• x parts by weight of component (b)
• y parts by weight of component (c)
• z parts by weight of component (d)
• u parts by weight of component (e) and
• v parts by weight of component (f).

The concentrations x and z preferably correspond at least to those required so that the aqueous monomer-containing dispersion remains sufficiently stable during the copolymerization; x is advantageously at least 0.002 and advantageously at most 15, preferably 0.005 to 10, but the cationic monomer is used in a molar excess over the anionic surfactant. The quantitative ratios of (a) and (b) given above refer to the respective components without taking into account the corresponding salt formation in the numbers 100 for (a) and x for (b), but should b) include; z is advantageously 0-80, preferably 1-80, particularly preferably 2-35. The preparations according to the invention are advantageously oil-containing and y is preferably 30-400, particularly preferably 40-300. The water content can fluctuate greatly and is partly also on the content of oil, i.e. depends on y, to the extent that the preparations according to the invention in the oil-containing form which have not yet been diluted with water, if they contain water, contain this predominantly in the discontinuous phase, i.e. Oil is the continuous phase and the water-containing phase is dispersed or emulsified in it. After the (inverse) emulsion polymerization, the water can be distilled off, advantageously azeotropically, in theory all the water can be distilled off, i.e. up to u = 0, but this is practically not preferred since it is difficult to completely distill off the residual water which swells the copolymer; on the other hand, the copolymer-containing W / O emulsion may optionally also contain water, e.g. also in the form of a further W / O emulsion or an aqueous solution of a copolymer (a), so that the water content of the preparation can also be relatively high; u is advantageously 0-600, preferably 1-600, particularly preferably 2-500. From an economic point of view, it is preferred not to distill off all the water and the water content u is advantageously 5 to 600, preferably 10 to 500.

In order to further facilitate the dispersibility of the polymer in water by dilution, it may be advantageous to add component (f) to the preparation, where (f) is used in the smallest possible amounts, in particular in amounts smaller than y the component ( f) is dissolved in component (c); v is advantageously 0-30, preferably 0-15.

• x = 0,002-15
• y = 30-400
• z = 1-80
• u = 1-600
• _v = 0-30, (wobei
  
  ) 3

The preparations according to the invention advantageously have the following composition: per 100 parts (a)

• x = 0.002-15
• y = 30-400
• z = 1-80
• u = 1-600
• _v = 0-30, (where
  
  ) 3

• x = x' = 0,005-10
• y = y' = 40-300
• z = z' = 2-35
• u = u' = 2-500
• v = v' = 0-15, und
  
  5

A particularly preferred composition of the preparations according to the invention is as follows: per 100 parts (a)

• x = x '= 0.005-10
• y = y '= 40-300
• z = z '= 2-35
• u = u '= 2-500
• v = v '= 0-15, and
  
  5

The oil-containing preparations according to the invention are dispersions which can have very different viscosities and it is also possible to produce very low-viscosity preparations; the viscosity (Brookfield rotational viscosity, measured in an LV viscometer) of the dispersions can be, for example, between 5 cp (spindle no. 2) and 10,000 cp (spindle no. 4), preferably between 50 cp (spindle no. 2) and 5,000 cp (spindle no. 4) vary; The dispersions according to the invention are also stable, ie they can be stored for a long time without modification, or, if the dispersions separate into layers, they can be brought into the original, regularly dispersed form by simple stirring. Particularly noteworthy is the very good dispersibility in water or dilutability with water of the preparations according to the invention, in particular the W / 0 emulsions, and indeed they can be diluted very quickly by simply adding the preparations to water or from water to the preparations with stirring or it is also possible to use the customary diluents, as are customary in the art and also described in large numbers in the literature, for a preliminary process thinning with water. Diluents which work with water jet pumps are particularly suitable, ie the copolymer dispersion is pumped through a nozzle and the water through another nozzle into a "chamber" in such a way that the water entrains the dispersion at high speed, after which the mixture in various ways, for example, distributed over baffle plates or walls or by using high shear forces or by pumping in and out in "rest tanks" or mixing chambers in the water.

Due to the very rapid dilutability with water of the preparations according to the invention, many large-scale, continuously carried out processes in which the cationic copolymers are used can be carried out very efficiently and with an optimal metering rate. It is also particularly worth mentioning that the preparations according to the invention can have a very high concentration of cationic polymers; the biological eliminability of the preparations can also be mentioned. The preparations according to the invention are notable for their dilutability with water and dispersibility in water, and the invention comprises such preparations in any concentration, provided that they can still be diluted with water or the copolymers are soluble or dispersible or dissolved or dispersed in water; in particular both preparations with a higher concentration are meant, in particular those which contain at least 10% by weight of cationic polymer, and also prediluted preparations, in particular those which contain at least 0.001% by weight, preferably at least 0.1% by weight, of cationic polymer.

The preparations according to the invention can be used in all fields of technology in which cationic water-soluble polymers are used, in particular they can be used as flocculants, primarily for flocculating aqueous suspensions; The preparations according to the invention are particularly notable for their retention properties and also have good drainage properties, and can therefore advantageously be used as retention and drainage agents for the production of cellulose fiber and cellulose structures. Another object of the invention is the use of the preparations according to the invention as a floc agents, preferably as retention and drainage agents for the production of cellulose fiber and cellulose structures, essentially cardboard and paper; they are also suitable as flocculants for aqueous sludge, especially digested sludge and fresh sludge from municipal wastewater treatment plants. The invention also relates to the process for the production of cellulose fiber or cellulose structures, in particular cardboard and preferably paper, which is characterized in that a preparation according to the invention is used as the retention and / or drainage agent.

A particularly homogeneous sheet formation can be observed in the production of paper, in particular in the continuous production of paper webs, using the preparations according to the invention.

The required concentration of the preparation for the respective application depends, of course, on the concentration of active substance (copolymer) for the respective flocculation. The pH during flocculation can vary in the usual ranges, mainly in the weakly alkaline to acid range depending on the field of application (preferably almost neutral).

In the following examples, the parts mean parts by weight and the percentages percent by weight, unless stated otherwise; the temperatures are given in degrees Celsius. Unless stated otherwise, the products used are commercially available products. Parts by weight relate to parts by volume such as g to ml.

example 1

16 parts of emulsifier (b ') are mixed with 1200 parts of water, resulting in a very fine, opalescent emulsion. Now 8 parts of calcium chloride are added from the emulsifier (b ') to form the calcium salt. A strong precipitation is immediately observed, which corresponds to the formation of the water-insoluble (oil-soluble) calcium sulfonate. Then 408 parts of White Spirit (c ') are added with stirring. A water-in-oil emulsion is formed which is stabilized by adding 27 parts of emulsifier (d ') becomes. This water-in-oil emulsion is then in the order given 120 parts of a 50% aqueous N, N-dimethylaminopropylmethacrylamide hydrochloride solution, 454 parts of acrylamide, 1.4 parts of ethylenediamine - tetraacetic acid disodium salt, 0.7 part of iron - (III) sulfate and 0.7 part of tert-butyl hydroperoxide are added. The pH of the aqueous phase is approximately 3.0. The dispersion obtained is then rendered inert with nitrogen and heated to 35 °. As soon as this temperature is reached, an air-free solution of 2.7 parts of sodium thiosulfate in 50 parts of water is started to be added dropwise. The addition takes place within 8 hours, the temperature being kept between 35 and 50 ° by cooling.

After the addition of the sodium thiosulfate solution, the polymerization reaction has ended. A stable, fine, low-viscosity polymer dispersion is obtained which has a viscosity of 1000 cp (Brookfield, spindle 3, 50 rpm). The product can be diluted very well with water; Approx. 30-40 seconds after the addition to cold water, the maximum viscosity is already reached with a 1: 200 (= 0.5%) aqueous dilution. The viscosity of a freshly prepared 1: 100 diluted (= 1%) aqueous preparation is approximately 500 cp (Brookfield, spindle no. 3, 60 rpm).

Example 2

97 parts of acrylamide, 28 parts of a 50% N, N-dimethylaminopropylmethacrylamide hydrochloride solution, 376 parts of water and 1 part of ethylenediamine-tetraacetic acid disodium salt are weighed into a 1500 volume part of reaction vessel. After everything is dissolved, the pH is adjusted to 3.0 with hydrochloric acid. A solution consisting of 8 parts of emulsifier (b '), 9 parts of emulsifier (d') and 202 parts of white spirit (c ') is then added to the monomer solution with thorough stirring. A thin, milky emulsion is formed. This is freed from atmospheric oxygen by evacuating three times to approx. 20 mbar and then releasing nitrogen. A nitrogen stream is passed over the emulsion for the entire duration of the polymerization. The mixture is now heated to 50 ° and 0.4 part of a, a'-azoisobutyronitrile, dissolved in 4 parts of acetone, is added under a strong stream of nitrogen. Allow to react for 3 hours at 50-55 °. To The emulsion becomes viscous and slightly exothermic for about 1/2 hour. The heating can be removed for about 1/2 hour. After 3 hours, a well pourable product is obtained. The viscosity is 250 cp (Brookfield, spindle No. 4, 50 rpm).

Example 3

4 parts of the emulsifier (b ') are mixed with 478 parts of water in a 1500 volume part of reaction vessel, a very fine, opalescent emulsion being formed. Now 0.75 parts of calcium chloride are added from the emulsifier (b ') to form the calcium salt. 97 parts of acrylamide, 28 parts of a 50% N, N-dimethylaminopropylmethacrylamide hydrochloride solution and 1 part of ethylenediaminetetraacetic acid disodium salt are then weighed out. After everything is dissolved, the pH is adjusted to 3.0 with hydrochloric acid. A solution consisting of 9 parts of emulsifier (d ') and 202 parts of white spirit (c') is then added to the monomer solution with thorough stirring. A thin, milky emulsion is formed. This is freed from atmospheric oxygen by evacuating three times to approx. 20 mbar and then releasing nitrogen. A nitrogen stream is passed over the emulsion for the entire duration of the polymerization. The mixture is now heated to 50 ° and 0.4 part of a, a'-azo-isobutyronitrile, dissolved in 4 parts of acetone, is added under a strong stream of nitrogen. The nitrogen flow can then be throttled again. Allow to react for 3 hours at 50-55 °. After about 1/2 hour the emulsion becomes viscous and slightly exothermic. The heating can be removed for about 1/2 hour. After 3 hours, a well pourable product is obtained. The viscosity is 350 cp (Brookfield, spindle No. 4, 50 rpm).

The preparations of the following composition are prepared analogously to Examples 1 to 3:

Example 4

• 96.5 parts of acrylamide,
• 11.5 parts of N, N-dimethylaminopropyl methacrylamide,
• 1 part of ethylenediaminetetraacetic acid disodium salt,
• 0.75 parts calcium chloride,
• 3.3 parts by volume of sulfuric acid,
• 14 parts of emulsifier (d '),
• 206 parts of odorless White Spirit (c '),
• 4 parts of emulsifier (b '),
• 0.4 parts of azo-isobutyronitrile dissolved in 4 parts by volume of acetone,
• 402.4 parts water
• Example 5
• 103.3 parts of acrylamide,
• 15 parts of a 50% solution of N, N-dimethylaminopropylmethacrylamide hydrochloride,
• 1 part of ethylenediaminetetraacetic acid disodium salt,
• 0.75 parts calcium chloride,
• 1.3 parts by volume of hydrochloric acid 1 n,
• 27 parts of emulsifier (d '),
• 110 parts of White Spirit (c '),
• 4 parts of emulsifier (b '),
• 0.4 parts of azo-isobutyronitrile dissolved in 2 parts by volume of chloroform,
• 478 parts of water

The viscosity of the freshly prepared, 1: 100 diluted (1%) aqueous preparation is approx. 350 cps (Brookfield, spindle no. 4, 100 rpm). The average molecular weight M _N (number average) is 2.1x10 ⁶ and M _W (weight average) is 10.5x10 ⁶ .

Example 6

• 96.5 parts of acrylamide,
• 48.0 parts of a 50% solution of N, N-dimethylaminopropylmethacrylamide hydrochloride,
• 1 part of ethylenediaminetetraacetic acid disodium salt,
• 0.75 parts calcium chloride,
• 3.3 parts by volume of sulfuric acid 1 n,
• 7 parts of emulsifier (d '),
• 6 parts of emulsifier (d "),
• 220 parts of White Spirit (c '),
• 4 parts of emulsifier (b '),
• 0.4 parts of azo-isobutyronitrile dissolved in 4 parts by volume of acetone,
• 380.4 parts water.

Example 7

• 107.7 parts of acrylamide,
• 6.3 parts of a 50% solution of N, N-dimethylaminopropylmethacrylamide hydrochloride,
• 1 part of ethylenediaminetetraacetic acid disodium salt,
• 0.75 parts calcium chloride,
• 1.75 parts by volume of hydrochloric acid 1 n,
• 27 parts of emulsifier (d '),
• 110 parts of White Spirit (c '),
• 4 parts of emulsifier (b '),
• 0.4 parts of azo-isobutyronitrile dissolved in 2 parts by volume of chloroform,
• 484.5 parts water.

Example 8

• 96.8 parts of acrylamide,
• 28.0 parts of a 50% solution of N, N-dimethylaminopropylmethacrylamide hydrochloride,
• 1 part of ethylenediaminetetraacetic acid disodium salt,
• 0.75 parts calcium chloride,
• 1.8 parts by volume of hydrochloric acid 1 n,
• 14 parts of emulsifier (d '),
• 206 parts of White Spirit (c '),
• 4 parts of emulsifier (b '),
• 0.4 parts of azo-isobutyronitrile dissolved in 4 parts by volume of chloroform,
• 386.7 parts water.

The viscosity of the freshly prepared, 1: 100 diluted (1%) aqueous preparation is approximately 200 cp (Brookfield, spindle No. 4, 100 rpm). The average molecular weight M _N (number average) is 2.4x10 ⁶ and M _W (weight average) is 8.9x10 ⁶ .

Example 9

• 110 parts of acrylamide,
• 0.53 parts of N, N-dimethylaminopropyl methacrylamide,
• 1 part of ethylenediaminetetraacetic acid disodium salt,
• 0.20 parts calcium chloride,
• 1 part by volume of hydrochloric acid 1 n,
• 6 parts of emulsifier (d "'),
• 14 parts of emulsifier (d '),
• 110 parts of White Spirit (c '),
• 1 part emulsifier (b '),
• 0.4 parts of azo-isobutyronitrile dissolved in 4 parts by volume of acetone, 485 parts of water.

Example 10

• 96.5 parts of acrylamide,
• 48.0 parts of a 50% solution of N, N-dimethylaminopropylmethacrylamide hydrochloride,
• 1 part of ethylenediaminetetraacetic acid disodium salt,
• 0.75 parts calcium chloride,
• 3.3 parts by volume of sulfuric acid 1 n,
• 9 parts of emulsifier (d '),
• 9 parts of emulsifier (d "),
• 220 parts of White Spirit (c '),
• 4 parts of emulsifier (b '),
• 0.4 parts of azo-isobutyronitrile dissolved in 4 parts by volume of acetone,
• 380.4 parts water.

The viscosity of the freshly prepared, 1: 100 diluted (1%) aqueous preparation is approx. 60 cp (Brookfield, spindle No. 4, 100 rpm); M _N = 1.7x10 ⁶ ; M _W = 11.4x10 ⁶ .

Example 11

• 131.0 parts of acrylamide,
• 15.6 parts of N, N-dimethylaminopropyl methacrylamide,
• 0.2 parts of ethylenediaminetetraacetic acid disodium salt,
• 0.75 parts calcium chloride,
• 10.6 parts by volume of hydrochloric acid (30%),
• 20.3 parts of emulsifier (d '),
• 87.5 parts of White spirit (c '),
• 101.9 parts of isoparaffin (c "),
• 3.8 parts of emulsifier (b '),
• 0.04 parts of 2,2'-azo-bis- (2-amidinopropane) dihydrochloride in 5 parts of water,
• 623.4 parts water.

The viscosity of the freshly prepared, 1: 100 diluted (1%), aqueous preparation is approx. 130 cp (Brookfield, spindle no. 4, 100 rpm); M _N = 2.2x10 ⁶ ; M _W = 9.9x10 ⁶ .

Emulsifiers used

• Emulsifier (b '): 62% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium salt, with a molecular weight of 440-470, in mineral oil
• Emulsifier (d '): C ₁₂ H ₂₅ (OCH ₂ -CH ₂ ) ₂ OH HLB = 6.5
• Emulsifier (d "): Sorbitan monooleate HLB = 4.0
• Emulsifier ( ^d "'): C ₁₈ -H ₃₅ (0-CH ₂ -CH ₂ ) ₃ OH HLB = 6.5

Oils used

• White Spirit (c '): aromatics-free terpenaline, boiling range 193-247 °, average molecular weight 173.
• Isoparaffin (c "): isoparaffinic oil, boiling range 210-260 °, aniline point = 88 °, isoparaffin content = 80%, density = 0.78.

Example of use A

• 70 Teile gebleichter Holzschliff
• 30 Teile gebleichter Sulfitzellstoff
• 15 Teile Kaolin.

A 1.5% aqueous paper pulp of the following solid composition is used:

• 70 parts of bleached wood pulp
• 30 parts of bleached sulfite pulp
• 15 parts of kaolin.

Before the sheet is formed on the Rapid-Koethen sheet former, 250 ml of test substance are removed from the test substance stock and mixed with 1% (based on ground wood and sulfite pulp) of a commercially available emulsion of a synthetic glue (emulsion of a dimeric alkyl ketene). Then 5.0 ml of a 0.05% aqueous solution of the product described in Example 8 and 750 ml of dilution water are added to the paper stock.

After a stirring time of 5 seconds at 250 rpm. the substance / water mixture is transferred into the filling chamber of the sheet former (Rapid-Koethen system), 3 liters of water being placed in the filling chamber. After a dwell time of 20 seconds, the sheet is formed by actuating the suction valve.

The sheet formed is very homogeneous and the filler retention is high. If the procedure is as described, but using. 20 ml (instead of 5.0 ml) of the 0.05% solution of the product from Example 8, the filler retention is even higher with homogeneous sheet formation.

The products of Examples 1-7, 8-11 are used in an analogous manner.

Example of use B

125 ml of a 1.5% aqueous paper pulp with the same solids composition as described in Example A are immediately mixed with 875 ml of water containing 5.0 ml of a 0.05% aqueous solution of the product described in Example 5 (approx 20 seconds) before the test and mixed on the Schopper-Riegler device.

A homogeneous paper sheet is obtained with rapid and good drainage. If instead of 5.0 ml 20 ml of the 0.5% solution of the product from Example 5 is used, the dewatering time is even shorter with homogeneous leaf formation.

The products of Examples 1-4 and 6-11 are used in an analogous manner.

Example of use C

133 g of an 8% digested sludge suspension from a municipal sewage treatment plant are mixed with 40 ml of a 0.2% aqueous solution of the product according to Example 8 in a measuring cylinder of 250 ml content and then on a Buchner porcelain nutsche, diameter coated with an Orlon filter 9 cm, filtered (gravity filtration); good dewatering of the sludge is obtained in a short time.

The products of Examples 1-7 and 9-11 are used in an analogous manner.

Example of use D

• 100 Teile gebleichter Sulfitzellstoff
• 20 Teile Calciumcarbonat

A 1% aqueous paper pulp of the following solid composition is used:

• 100 parts of bleached sulfite pulp
• 20 parts calcium carbonate

Before the sheet is formed on the Rapid-Köthen sheet former, 250 ml of test substance are removed from the test substance stock and mixed with 1% (based on the sulfite pulp) of a commercially available emulsion of a synthetic glue (emulsion of a dimeric alkyl ketene). Then 2.5 ml of a 0.05% aqueous solution of the product described in Example 8 and 750 ml of dilution water are added to the paper stock. After a stirring time of 5 seconds at 250 rpm. the substance / water mixture is checked in the filling chamber of the sheet former (Rapid-Koethen system), 3 liters of water being placed in the filling chamber. After a dwell time of approx. 20 seconds, the sheet is formed by actuating the suction valve.

With good filler retention, homogeneous leaf formation is observed. If this process is repeated, but using 5, Oml, 7.5m1 and 10.0ml of the 0.05% aqueous solution of the product from Example 8, an increase in retention is observed with homogeneous leaf formation.

The products of Examples 1-7 and 9-11 are used in an analogous manner.

Application example E

• 100 Teile gebleichter Sulfitzellstoff
• 20 Teile Kaolin
• 3 Teile Harzleim
• 2 Teile Aluminiumsulfat

A 2% aqueous paper pulp of the following solid composition is used:

• 100 parts of bleached sulfite pulp
• 20 parts of kaolin
• 3 parts of resin glue
• 2 parts of aluminum sulfate

Before the sheet is formed on the Rapid-Koethen sheet former, 250 ml of test substance is mixed with 5 ml of a 0.0125% aqueous dilution of the product according to Example 8 and with 750 ml of dilution water. After a stirring time of 5 seconds at 250 rpm. the substance-water mixture is transferred into the filling chamber of the sheet former (System Rapid-Koethen), in which Filling chamber 3 1 water are submitted. After a holding time of 20 seconds, the sheet is formed by actuating the suction valve; after the test sheets have been formed, they are ashed.

The products of Examples 1-7 and 9-11 are used in an analogous manner.

Homogeneous leaf formation is observed with high filler retention. By repeating this procedure, but in accordance with the use of 10m1, 15m1 and 20ml of 0.0125% aqueous dilution of the product Example 8, it is observed in each case with a homogeneous sheet formation, an increase in the filling _- retention material.

Claims (17)

1. Water-dilutable, polymer and surfactant-containing preparations, characterized in that they
as polymer (a), a cationic copolymer (a _l ) acrylic and / or methacrylamide and (a ₂ ) a monomer of the formula

wherein R _{1 is} hydrogen or methyl, R _{2 is} methyl or ethyl, R _{3 is} methyl or ethyl and n is 2 or 3,
contain, the molar fraction of (a ₁ ) in the copolymer making up 91 to 99.8 mol% and the molar fraction of (a ₂ ) in the copolymer making up the remaining 9 to 0.2 mol%,
contain an anionic surfactant as the surfactant (b), the molar fraction of anionic surfactant (b) being not greater than the molar fraction of cationic monomer units of the copolymer (a) and part of the cationic monomer units of the copolymer with the anionic surfactant (b) can be combined to form salt, and contain as oil (c) a water-immiscible oil in which the polymer is not soluble but is finely divided therein. 2. Preparations according to claim 1, characterized in that the anionic surfactant (b) is a sulfonated hydrocarbon. 3. Preparations according to claims 1-2, characterized in that they are further essential components (d) a lipophilic or oil-soluble, non-ionic surfactant and / or (e) water and optionally (f) a polar solvent which is miscible with oil, sparingly soluble in water and not self-dispersible, which alone has no emulsifier properties, but lowers the interfacial tension between water and oil
contain. 4. Preparations according to claims 1-3, characterized in that (c) is a mixture of oils (c _l ) and (c ₂ ), which is chosen such that the O / W EHLB value of (c _l ) is greater than the 0 / W-EHLB value of the mixture (c ₁ ) ⁺ (c ₂ ). 5. Preparations according to claims 1-4 containing at least 0.001% by weight, advantageously at least 0.1% by weight, preferably at least 10% by weight of component (a). 6. A process for the preparation of preparations according to claim 1, characterized in that the copolymer is mixed with the anionic surfactant (b) and the oil (c) before, during or after the polymerization. 7. The method according to claim 6 for the preparation of preparations according to claims 1-5, characterized in that a) an oily dispersion containing a hydrophilic, cationic polymer (a), water (e) and a lipophilic or oil-soluble, non-ionic surfactant (d), with a lipophilic or oil-soluble, practically water-insoluble, anionic surfactant (b ₂ ), where (b ₂ ) is a sulfonated hydrocarbon, optionally in salt form, and the oil of the oily dispersion is an oil ( _C3 ), ie a water-immiscible hydrocarbon oil in which the polymer (a) is not soluble, but is finely distributed therein with the water, and optionally adds component (f) together with (b ₂ ) and / or (b ₂ ) as a solution in the oil (c ₃ ); or β) the monomers required to form the cationic polymers (a) are polymerized in the presence of anionic surfactants in a W / O emulsion and, if desired, water and / or oil are distilled off and, if appropriate, further additives (a), (b), (c), ( d), (e) and / or (f), some of the cationic monomers optionally being present as monomer salts of anionic surfactants. 8. Use of the preparations according to claims 1-5 as a flocculant. 9. Use according to claim 8 in the manufacture of paper. 10. Use according to claim 8 or 9, characterized in that the preparations according to claims 1-5 prediluted and used in the prediluted form for flocculation. 11. Use according to claim 10, characterized in that the preparations according to claims 1-5 are continuously prediluted and metered in continuously for the production of paper. 12. A process for the production of structures from cellulose fibers, by dewatering a corresponding pulp, characterized in that a preparation according to claims 1-5 is added to the aqueous pulp. 13. The method according to claim 12 for the production of paper. 14. The products manufactured according to claims 12-13. 15. Flocculant characterized by a content of components a), b) and c) and optionally d), e) and / or f) as defined in claims 1-5.